Cellulosic textile shrinkage control and crease resistance with inhibited tenderizing action



Patented Feb. 13, 1951 CELLULOSI C TEXTILE SHBINKAGE CON- TROL AND'CREASE RESISTANCE WITH INHIBITED TENDERIZING ACTION Leo Beer, Providence, R. L, assignor to Alrose Chemical Company, Cranston, R. 1., a corporation of Rhode Island No Drawing. Application May 23, 1947, Serial No. 750,159

. 1 This invention relates to the treatment of textile materials of natural or regenerated 081111 lose, or mixtures thereof, or mixtures with limited amounts of cellulose esters of organic acids,

in any form to impart shrink-proofing, creaseproofing, or crush-proofing properties thereto yet incurring little loss in tensile strength or abrasion resistance.

The treatment of cotton and regenerated cellulose fabrics with aldehyde type compounds for such purposes as shrinkage control and creaseproofing is a means which is well known in the textile fiber industry. In the conventionally employed process where satisfactory results have been secured, wherein the fabrics have been treated with aldehydes'or compounds which split aldehydes oil, a strongly acidic catalyst or a salt which is either acidic or becomes acidic during baking at elevated temperatures is required. This results in deterioration in tensile strength and abrasion resistance which is especially serious in the case of cottons.

By a more recent development, cellulosic fibers and fabrics have been treated by a process characterized by the employment of glyoxal, and,

wherein oxalic acid is the catalyst. But where-- as rayon fabrics are made shrink-proof and the shrinkage tendency significantly curbed in cotton fabrics, the former displays a loss in the range of 20% in tensile strength, and the latter in the range of 50%.

12 Claims. (Cl. 8-1164) trations of the glyoxal are employed to obtain crease-proofing effects. This loss in tensile strength is not as great as in the case of the acid catalysts employed with aldehyde impregnating solutions of the prior art, but-it still may be objectionable at this high temperature, espeecially on-fabrics containing cotton.

Basic aluminum salts such as aluminum acetate have been used in the prior art for such purposes as decreasing the deleterious tenderizing.

effect of acidic catalyst in the aldehyde treatment of cellulosic textile materials; but, as is evident from the tests shown in the examples infra on embodiments of the present invention, the action of basic aluminum acetate alone is inadequate. Sodium chloride alone has also proven relatively ineffective.

My U, S. Patent #2,484,545 issued October 11, 1949, reveals that, by using as catalyst certain substantially neutral, water-soluble alkali metal salts having oxidizing properties in aqueous solu tion, such as an alkali metal chlorate, with an aqueous solution of glyoxal as the impregnating solution, shrinkage control is obtained with a reduction in the loss in tensile strength or abrasion resistance on natural cellulosic type or the regenerated cellulose type fabrics; this is even true of cotton.

However, it has been found that, even when the above mentioned oxidizing salts are employed in place of acid-catalysts, a certain loss in tensile strength and abrasion resistance, as well as discoloration of the fabric results, if the baking temperature rises to 150 0., or if higher concen- It is an object of the present invention to treat natural cellulosic textile materials as well as regenerated cellulose textile materials or mixtures thereof or with cellulose esters of organic acids containing up toabout 50% of cellulose ester fibers with aqueous solutions of aliphatic aldehyde-type compounds in the presence of either an acid catalyst or acid or potentially acid salt catalyst, but with the addition of alkali metal sulfates, wherein the textile materials after the conventional succeeding steps of squeezing, drying, and curing exhibit but small loss in tensile strength or abrasion resistance.

' Broadly speaking, my invention consists in employing an alkali metal sulfate in the treat- 'ment of the cellulosic textile material. with an aqueous solution of an aliphatic aldehyde-type compound to greatly inhibit the tenderizing action of the acid'catalyst, acidor potentially acid salt catalyst, each of whichis used in such processes, wherein either shrinkage reduction or crease-proofing is achieved. Even very small quantities of these sulfate salts of the order of 0.1% have a marked effect on preserving the original tensile strength. Needless to say, those concentrations above 5 to 10%, which may interfere with shrinkage control or crease-proofing, should be avoided,

According to my invention, by which the aforesaid disadvantages are eliminated, any form of the textile materials of the types described infra are thoroughly impregnated with an aqueous solution of an aliphatic aldehyde-type compound, a catalyst of the aforementioned type which is defined specifically below, and an alkali metal sulfate, which solution may or may not also contain a small amount of basic aluminum acetate or other water soluble basic aluminum salts, such as basic aluminum formate. The textile material is then squeezed, pressed or centrifuged allowing a pick-up of a predetermined percentage, such as liquid retention, on the basis of the dry goods. It is then dried and finally cured or baked. A drying range of 70-95 C., and a baking temperature within -150 C., is usually preferred. However, the exact formulation of the solution as to components and concentrations, as Well as the conditions of drying and baking may vary depending upon the construction, composition, and form of the textile material. After curing, the fabrics are rinsed and secured, extracted and dried before putting into industrial channels of trade or before making the physical measurements referred to in the comparative tests below. These steps sub-- sequent to the curing form no point of my invention. v

The step of impregnating the fibers with the aqueous solution of the aldehyde-type compound, catalyst, and alkali metal sulfate, may take place at any time subsequent to the desizing of the material which is to be treated. It can be upon the raw stock, skein or on the woven or the knitted piece. But all traces of starch, gums or natural resins and other sizing agents should be removed for optimum results in order to permit this aqueous treating solution to penetrate the fibrous material and enter the heart of the fibers.

Where shrinkage control of fabrics is desired, the dimensions at which the fabric is finally dried after the baking and subsequent finishing operations must be predetermined by a preliminary wash test. If shrink-proofing and crush-proofing are both desired this dimensional control is also necessary, but if only crush-proofing, this control is not necessary.

The textile materials which may be treated by the invention set forth herein include natural cellulosic fibers, regenerated cellulosic fibers, and mixtures of any of the aforesaid type fibers with each other or with cellulose ester fibers of organic acids, provided such mixtures do not contain more than about 50% of cellulose acetate. The foregoing textile materials may be treated in theform of filaments, fibers, yarns, woven fabrics, knitted fabrics, or any other forms. By the term natural cellulose I means such fibers as cotton, linen,

hemp, jute, etc. By the term regenerated cellulose I mean viscose or cuprammonium rayon. Cellulose acetate is the only ester of cellulose with an organic. acid commercially available at reasonable prices but cellulose propionate or other cellulose esters of short chain aliphatic acids would be suitable.

The term aliphatic aldehyde-type compounds as employed herein including the claims is used to designate simply monoor polyaldehydes and compounds'of these aldehydes which yield watersoluble free aliphatic aldehydes in substantial amounts, not simply traces, by a subsequent baking; this would include polymeric aldehydes, acetal-type compounds, and aldehyde-ammonia or aldehyde-amine or aldehyde-bisulfite compounds. Thus, suitable compounds would include formaldehyde, trioxymethylene, paraformaldehyde, and hexamethylene tetramine. Other aliphatic aldehydes such as acetaldehyde,.propionaldehyde, crotonaldehyde, etc., could obviously be employed. Polyaldehydes such as glyoxal and glycerol dialdehyde, as well as polygloyxal, tetrahydroxy dioxane and glyoxal-bisulfite can be used. This definition would exclude of course precondensates of either urea and its derivatives or melamine and its derivatives with aldehydes.

By acid or potentially acid salt is meant, respectively, a salt which is acidic in aqueous solution or which becomes acidic at such elevated temperature as 120 C. or somewhat higher. Among the acid catalysts which may be used are the non-volatile organicacids: oxalic acid, tartarto acid and citric acid. Mineral acids, such as hydrochloric, sulfuric, and phosphoric acids are not preferably used because of the danger of attacln'ng the fabrics.- Examples of suitable acid salts are sodium bisulfate and mono-sodium phosphate. Ammoniumsalts of those organic and inorganic acids, such as diammonium phosphate and ammonium chloride which give off ammonia upon baking, are examples of those salts which become acid upon heating. A fixed alkali salt which becomes acid on baking due to forming hydrochloric acid is sodium chloro-acetate. Mixtures of catalysts from two or more of the above classes may be used according to the intent of this invention.

If desired the hand. or body of the goods treated can be modified in the direction of either a softer or a stifl'er finish at will by the introduction to the impregnating bath of suitable agents, such as cation softeners for the former effect, or such vegetable or animal colloids as starches, gums, glues, gelatins and modified starches for the latter effect. But the process of this invention is carried out in the absence of any phenolic or amidic compounds capableof forming resinous bodies with aldehydes under the conditions. Therefore, fabrics treated by my method show no tendency toward chlorine retention.

Fabrics of the natural cellulosic type or of the regenerated type treated by my invention herein are stabilized against laundering shrinkage, or rendered crease-resistant depending on concentration of impregnating bath and method of handling. The superior nature of this process can be appreciated when, moreover, it is realized that the effects so obtained are permanent, and even successive washings at the boil do not affect the results.

The following specific examples serve to illustrate the results obtained by my process:

EXAMPLE 1 Formaldehyde+oxalic acid treatment of Cotton Spun rayon An x 80 cotton sheeting and a spun rayon fabric were treated respectively for the purpose of obtaining shrinkproof effects with aqueous solutions of the following compositions, one of which it will be noted contains sodium sulfate (denoted by letter b); the check (denoted by letter a) does not:

[Formula in comvrma] Gms. Gm. Formaldehyde 38% 120 xalic acid 8 Sodium sulfate, anhydrous. 20 Water to 1 liter.

Table I.Tensile strengthwarp direction I Spun Cotton Rayon Pound. Pound-v Untreated 51 68 Treated with (a) 26 33 V Treated with (b) 31 68 OBSERVATIONS I From Table I it will be seen that in the case of both cotton and rayon when a solution of formaldehyde and oxalic acid was employed without the presence of sodium sulfate, there was a loss of 50% of its tensile strength, whereas with it there was no loss in the latter type fabric and on cotton a restoration of 8/25, i. e., 32% of the tensile strength loss it would have sustained if sodium sulfate had not been used.

EXAMPLE2 v Glyoxal+oxalic acid treatment of:

Cotton Dyed spun rayon [Formula in common] Gms. Glyoxal 30% 70 Oxalic acid 4 Aluminum acetate, basic (7.6% A1203) 2 Water to 1 liter Sodium chloride or sodium sulfate as indicated in Table II The respective fabrics were immersed in the solutions of the composition indicated, after which they were squeezed to 100% liquid solution retention. They were then dried at 80-95 C., without tension and baked for 6 minutes at 135" C. They were scoured 10 minutes at 50-60 C., rinsed, hydroextracted and dried without tension.

Both tensile strength tests and laundering tests were run on the samples; by the latter the degree of shrinkage control was determined. The laundry tests were carried out in a rotary wheel following the' procedure in commercial standard 0859-44.

two launderings. In the table below the values in the columns under Warp Shrinkage indicate increase in length, and values in these two columns with no indication, indicate decrease in length.

Table 11 Type of Salt Warp Shrinkage 5 5,

Added (in (Process-+2 g abs 2 grams) washes) Grab Test) N 2101 Na;S 52 Cotton Egg Cotton Per cent Per cm! Untreatedh" 4. 4 3. 6 69 44 Treated l 0 l. l 48 18 Treated 2-- 2 +1 1.6 62 34 Treated 3.. 4 +0. 3 l. 8 67 38 Treated 4 6 0.8 2 73 31 Treated 5 +1. 7 l. 1 49 16 Treated 6 +0. 8 0. S 49 16 Treated 7 +1. 4 0. 8 49 16 Treated 8 +1. 3 0. 8 49 16 OBSERVATIONS Excellent shrinkage control is obtained in all treatments of this above common formula, both without as well as with sodium chloride or sodium sulfate.

The pronounced loss of tensile strength of The shrinkage measurements below represent the overall shrinkage in processing plusis in contrast to samples #2, 3. and 4,'where by the use of sodium sulfate, the tensile strength is vastly improved as compared therewith. This is true for cotton as well as for the rayon. But

samples #5, 6, '7, and 8 show that sodium chloride has n appreciable eflect up to 10 grams/liter (not etermined in higher concentrations) EXAMPLE 3 Glyoxal+sodium chlorate treatment of:

Cotton Spun rayon Samples of cotton (80 x 80 cotton sheeting) and spun-rayon were treated, for the purpose of making quantitative measurements on the shrinkage, tensile strength and abrasion resistance, with aqueous solutions-of the following four different compositions, one of which does not contain sodium sulfate but all of which contain basic aluminum acetate.

I Formulae:

, GM. 01113. Gm. Gms. Glypxal, 50 50 60 96 Sod um chlorate 5 5 5 5 Basic aluminum acetate (7.6% AlO;) 2 2 2 2 Sodium sulfate 100 50 80 Water to 1 liter.

'I'he'respective fabrics were immersed in the solutions of the above indicated compositions,

after which they were squeezed to liquid retention, dried at 80-95 C., without tension, and

baked as follows:

1 and 2--baked 6 minutes at C. 3a and4a-baked 3 minutes at C. 3b and lb-baked 5 minutes at 135 C. 30 and 4c-baked -'7 minutes at 135 C.

The fabrics were then scoured, rinsed and dried as in the foregoing examples. Tests were conducted upon the samples, results on which are iven;

Table III Tensile strength (Grab Testffg j gg pounds) Taber abrasion s resistlance pun cyc es, Comm Rayon Spun s Rayon Cotton I 355 W F W F Per cent Per cent Untreated 49 36 62 51 400 .5 Treated #1.-- 35 Treated #2-.. 50 Treated#3l 47 34 62 425 35 3.3 Treated #3b 49 35 63 53 425 3 2 2.3 Treated#3c 1 49 35 63 55 38 2.0 Treated #4a- 49 35 62 52 35 1.7 Treated #4b. 48 38 62 51 3 7 2.6 Treated #4c 46 35 63 50 425 1.7

indimtes warp direction; F indicates filling. Measurements in each are in pounds.

OBSERVATIONS sample #1, where no sodium sulfate is employed. 7:; the diiferent quantities of this salt.

Where'sodium sulfate was present the abrasion resistance was in fact slightly improved over the untreated sample.

EXAMPLE 4 Glyoxal with various catalysts using sodium and potassium sulfates: Cotton Samples of cotton sheeting (80 x 80) were treated to obtain crease-resistance and shrinkage control while determining quantitatively the tensile strengths, wherein an aqueous solution of glyoxal, basic aluminum acetate and a catalyst of either sodium chlorate or an acid was used in conjunction with sodium sulfate or potassium sulfate.

The cotton sheeting samples were immersed in the below identified solutions, all of which were made up to 1 liter, after which they were squeezed, dried, baked and washed as described in the preceding examples, except as to the time and temperature of baking indicated below. Table IVa represents the composition by solution and therefore sample number, and Table IVb the tensile strength by corresponding sample number for three distinct baking conditions, hence twenty-four samples.

Table IVa Table Va Cotton Spun Rayonand Cotton, figfg Treated Samples 5 l l 2 3 l 4 i 5 l 6 61m 01m. Gms. Gm. Gma. Gms. Glypxal,80% 50 50 50 50 50 50 Sodium Sulfate 50 O 0 50 100 Sodium Chlorate..- 5 5 5 5 5 5 Basic Aluminum Acetate (7.6% A120!) 2 0 2 2 2 2 Water to 1 liter.

Table Vb.Tensile strength (warp) (Grab test pounds) 1 2 Untreated 3 4 5 6 Untreated EXAMPLE 6 Sodium chlorate+oxalic acid to obtain greaseproofing: Spun rayon A spun rayon fabric was treated to obtain crease-resistance using aqueous solutions of the Glyoxal, Sodium Chlorate Tartaric Acid Citric Acid Sodium Sulfate Potassium Sulfate".-- Basic Aluminum Acetate AhO;) 3 3 3 3 3 Table IVb.Tensile strength (Grab test in poundswarp only) [Untreated shecting=55 lbs.]

Sheeting Treated Having Bake 6min. at 135 0 2c 41 45 51 a min. at 150 0 2s 51 as 48 5o 5 min. at 150 0 24 4s 31 51 52 OBSERVATIONS The loss of tensile strength incurred by the use of oxidizing catalysts is overcome by the use of either potassium sulfate or sodium sulfate. Longer heating at 150 C., which is a high cur temperature, gives for the acidic catalyst without these sulfates distinct weakening to the cotton fabric.

EXAMPLE 5 Glyoxal-l-sodium chlorate+sodium sulfate:

Cotton Spun rayon cotton fabric Samples of an x 80 bleached cotton sheeting and 80/20 spun rayon cotton fabric were treated to obtain shrinkage control, and to secure quantitative measurements of the tensile strength. They were immersed in aqueous solutions of the composition indicated in Table Va below, after which they were squeezed, dried, baked and washed and dried as described in the preceding examples. The tensile strength measurements made on them appear in Table Vb.

' 5 Table Vla I 1 I 2 I 3 I 4 GM. Gnu. Gms. lmrv (llyoxal I30%). 300 300 300 300 Sodium Chlorate. 15 15 l5 l5 Oxalic Acid 10 10 10 10 Sodium Sulfate 0 10 20 30 Basic Aluminum Acetate (7.6% A110, 4 4 4 4 Water to 1 liter.

' Table VIb.--Tensfle strength (Grab test in poundswarp only) 1 2 3 4 Untreated GENERAL OBSERVATIONS EXAIMPLE'I Giyoxal-i-oxalic acid or sodium chlorate+sodium sulfate:Vat dyed spun rayon and cotton fabric A sample of vat dyed fabric (5.5% spun high tenacity rayon 45% cotton) was treated to obtain shrinkage control. 7 solution of the composition indicated in Table VH4: below, after which it was squeezed, dried, baked, washed and dried, as described in the preceding example.

Table VH -Formulations Glyoxahm, gms 70 70 70 oxalic Acid, gms 4 4 0 0 um Chlorate, gms 0 0 7 M 736 Sodium Sulfate, anhydn, gins. 0 6 0 50 Basnilc'Alumm um Acetate (7.6% A1101), 2 2 2 2 Water to 1 liter.

Table VIIb.-Shrinkage tests Tensile Strength W (After 3 Washes) F 24 Abrasion Resistance. 190 335 OBSERVATIONS Sodium sulfate allows shrinkage control without impairing tensile strength both with oxalic. acid and with sodium chlorate as catalyst.

In the method of the present invention 1% of glyoxal (3.3% of commercial 30% aqueous glyoxal) will result in some shrinkage control. Customarily about 5-7% of 30% aqueous glyoxal is employed for shrinkage control. For crease-resistance about 10-30% of this 30% strength glyoxal is employed. In either case the quantity will depend upon the nature and construction of the textile material.

It was impregnated with a 10 I The temperature of impregnation is not critical, and the solution may be applied at room temperature or it may be heated to facilitate penetration.

While a range of C., is preferred for the drying after impregnation and squeezing, the ambient temperature may actually range from room temperature up to the baking temperature employed in the subsequent step. The temperature of the cloth itself does not rise above C., until substantially most of the water is given olf. The drying and baking steps may be performed as two separate operations or may be combined into one operation. The preferred baking or curing temperature is -150 C., but this may vary from substantially 120 to 175 C. The time of baking varies inversely with the temperature of baking. To illustrate, in the case of one particular fabric a period of 6 minutes was employed at C., but only 2 /23 minutes at C.

The quantity of acid catalyst, acidor potentially acid salt, catalysts required will vary, depending upon the nature of the particular catalyst, the amount of glyoxal employed, and other factors. Where oxalic acid is used about 5-6% in reference to the weight of commercial glyoxal is preferred for conferring shrink-proofing properties.

The amount of alkali metal sulfate should not be less than 0.1% of the total weight of solution. It is preferably about 0.5% in combination with oxalic acid.

The use of basic aluminum salts of volatile organic acids is optional, but it appears to contribute slightly to the improvement in tensile strength obtained by its conjoint use with alkali metal sulfates. While various basic aluminum salts of volatile organic acids may beused, I prefer to employ basic a uminum acetate or formate. I have found 0.2-0.4% of the weight of the solution satisfactory. But higher proportions interfere with the catalytic reaction.

While this invent on has been described with reference to particular embodiments and specific examples, I do not intend that my invention shall be limited to such embodiments and examples except as hereinafter described in the appended the steps of impregnating textile materials of the group consisting of natural cellulose, regenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile materials are substantially free from sizing agents, with an aqueous solution of an aliphatic aldehyde type compound, at least 0.1% but not over 10% of an alkali metal sulfate and a small amount of a member of the group consisting of a water-soluble non-volatile organic acid, an acid salt and a, potentially acid salt, removing surplus liquid from the textile material drying it until most of the water has been 're-' moved and baking at substantially 120-175 C., wherein the kind and amount of aldehyde-type compound is at least suflicient to confer shrinkage reduction on the textile material.

2. In the process .of treating woven textile fabrics, the steps of impregnating woven textile fabrics made of fibers from the group consisting of natural cellulose, regenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile materials are substant a y free from s'izin ag nts, with an aqueous solution of an aliphatic aldehyde type com ound, at least 0.1% but not over 10% of an alkali metal sulfate and a small amount of a member of the group cons sting of a water-soluble nonolatile or anic acid. an acid salt and a potent allv ac d salt. removing sur lus liquid from the textile material. dr ing it unt l mo t of the water as een removed and baking at suhsta t al v I'm- 75 0., wherein the kind nd a o nt of aldehvd-tvne com ound is at lea t suflicient to confer crease resistance on the fabric.

3. In the process of treatin textil mate ials, the steps of im re nat n t xt e mater als of the grou consi tin of natu al ce lulo e. r enerated ce lulose and mixtur s with each other and u to 50% of ce lu o e esters of or anic acids. which textile mater a s are uhstant a v free from sizin agents. w t an a u ous solution of forma dehvde. at least 0.1% but n t o er "10% of an alkali metal sulfate and a. small amount of a member of t e. groun con i ting of a water-soluble nonvolat le or an c ac d. an acid sa t a d a pot ntial acid sa t. re ovin 'sur'o us iouid from the textile materia dry n it until most of the w ter has be n remo ed and baking at sub t ntially 120-1'75 (3.. er n the a ount of formaldehvde is at lea t suflicient to confer shrinkage reduction on the t ti e m t rial.

4. In t e p oc ss o tr ating woven textile fa r cs. the stens of impregnatin woven textile fabrics made of fibers from the ro con istin of natural nl1ulose., re enerat d cellulose and m tures with each other and up to 50% of cell lose. est rs of or an c ac ds. which te tile materials are substantiallv free from si ng a ents, with an aqueous solution of ormaldehvde. at least 0.1% b t not over 10% of an alkali metal sulfate and a s all amount of a member of the roup consisting of a wat rsol ble non-vol tile or an c acid. an acid salt and a potentiallv acid salt. r moving surp us liqu d from the textile material, drving it until most of the ater has been removed and baking at substantially 120-1'75 0.. wh in the amount of forma d h de is at le st sufllcient to confer creas resistance on t e fabric.

5. In the process of treating textile materials, the steps of impre nating textile materials of the group consisting of natural cellulose, regenerated cellulose and mixtures with each oth r and up to 50% of cellulose esters of organic acids. which textile materials are substantially free from sizing agents, with an aqueous solution of elvoxal, at least 0.1% but not over 10% of an alkali metal sulfate and a small amount of a member of the group consisting of a watersoluble non-volatile organic acid, an acid salt and a potentially acid salt, removing surplus liquid from the textile material, drying it until most of the water has been removed and baking at substantially 120-175 0.. wherein the amount of formaldehyde is at .least sumcient to confer shrinkage reduction on the textile material.

6. In the process of treating woven textile fabrics, the steps of impregnating woven textile fabrics made of fibers from the group consisting of natural cellulose. regenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile materials are substantially free from sizing agents, with an aqueous solution of glyoxal, at least 0.1% but not over of an alkali metal sulfate and a small amount of a member of the group consisting of a water-soluble non-volatile organic acid, an acid salt and a potentially acid salt, removing surplus liquid from the textile material, drying it until most of the water has been removed and baking at substantially C.. wherein the amount of formaldehyde is at least sufflcient to confer crease resistance 011 the fabric.

7. In the process of treating textile materials, the steps of impregnating textile materials of the group consisting of natural cellulose, regenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile materials are substantially free from sizing agents, with an aqueous solution of hexamethylene tetramine, at least 0.1% but not over 10% of an alkali metal sulfate and a small amount of a member of the group consisting of a water-soluble non-volatile organic acid, an acid salt and a, potentially acid salt. removing surplus liquid from the textile material, drying it until most of the water has been removed and baking at substantially 120-175 C.. wherein the amount of hexamethyl ne tetramine is at least sufficient to confer shrinkage reduction on the textile material.

8. In the process of treating woven textile liquid from the textile material, drying it until most of the water has been removed and baking at substantially 120l75 0., wherein the amount of hexamethylene tetramine is at least sufficient to confer crease resistance on the fabric.

9. The process set out in claim 1 wherein the alkali metal sulfate is sodium sulfate.

10. The process set out in claim 2 wherein the alkali metal sulfate is sodium sulfate.

11. In the process of treating textile materials, the steps of impregnating textile materials of the group consisting of natural cellulose, rcgenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile materials are substantially free from sizing agents, with an aqueous solution of an aliphatic aldehyde type compound, at least 0.1% but not over 10% of an alkali metal sulfate, a water-soluble basic aluminum salt of a volatile organic acid, and a small amount of a member of the group consisting of a watersoluble non-volatile organic acid, an acid salt and a potentially acid salt, removing surplus liquid from the textile material, drying it until most of the water has been removed and baking at substantally 120-175 C., wherein the kind and amount of aldehyde-type compound is at least sufiicient to confer shrinkage reduction on the textile material.

12. In the process of treating woven textile fabrics, the steps of impregnating woven textile fabrics made of fibers from the group consisting of natural cellulose, regenerated cellulose and mixtures with each other and up to 50% of cellulose esters of organic acids, which textile 13 materials are substantially free from sizing agents, with an aqueous solution of an aliphatic aldehyde type compound, at least 0.1%, but not over 10%, of an alkali metal, sulfate, a watersoluble basic aluminum salt of a volatile organic acid, and a small amount of a member of the group consisting of a water-soluble non-volatile organic acid, an acid salt and a potentially acid salt, removing surplus liquid from the textile material, drying it until most of the water has been removed and baking at substantially 120- 175 0., wherein the kind and amount of aldehyde-type compound is at least suflicient to confer crease resistance on the fabric.

LEO BEER.

' file of this patent:

Number Number 14 UNITED STATES PATENTS Name Date Eschalier June 20, 1911 Hollander Aug. 3, 1926 Palmer et a1. June 2, 1931 Becker Sept. 2'7, 1932 Lilienteld Jan. 29, 1935 Heckert May 11, 1937 Wolf et al Feb. 15, 1938 Beer Oct. 11, 1949 FOREIGN PATENTS Country Date Great Britain Jan. 22, 1937 

1. IN THE PROCESS OF TREATING TEXTILE MATERIALS, THE STEPS OF IMPREGNATING TEXTILE MATERIALS OF THE GROUP CONSISTING OF NATURAL CELLULOSE, REGENERATED CELLULOSE AND MIXTURES WITH EACH OTHER AND UP TO 50% OF CELLULOSE ESTERS OF ORGANIC ACIDS, WHICH TEXTILE MATERIALS ARE SUBSTANTIALLY FREE FROM SIZING AGENTS, WITH AN AQUEOUS SOLUTION OF AN ALIPHATIC ALDEHYDE TYPE COMPOUND, AT LEAST 0.1% BUT NOT OVER 10% OF AN ALKALI METAL SULFATE AND A SMALL AMOUNT OF A MEMBER OF THE GROUP CONSISTING OF A WATER-SOLUBLE NON-VOLATILE ORGANIC ACID, AN ACID SALT AND A POTENTIALLY ACID SALT, REMOVING SURPLUS LIQUID FROM THE TEXTILE MATERIAL, DRYING IT UNTIL MOST OF THE WATER HAS BEEN REMOVED AND BAKING AT SUBSTANTIALLY 120-175* C., WHEREIN THE KIND AND AMOUNT OF ALDEHYDE-TYPE COMPOUND IS AT LEAST SUFFICIENT TO CONFER SHRINKAGE REDUCTION ON THE TEXTILE MATERIAL. 